CN110152665B - CuO/Cu2Preparation method of O/Cu ternary composite material - Google Patents
CuO/Cu2Preparation method of O/Cu ternary composite material Download PDFInfo
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- 238000001514 detection method Methods 0.000 description 6
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- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
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- 229910052802 copper Inorganic materials 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 3
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 description 3
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 3
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 3
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- 238000010521 absorption reaction Methods 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
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- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
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- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 1
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- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/36—Biochemical methods
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The invention provides a CuO/Cu2The preparation method of the O/Cu ternary composite material comprises the following steps: respectively preparing a copper salt solution and an alkali liquor; adding yeast into water for culturing, and adding the yeast into a copper salt solution and an alkali liquor in sequence after culturing to obtain a mixed solution; heating the mixed solution for reaction to obtain a reaction solution; drying the reaction solution, calcining, cooling to room temperature, and calcining again to obtain CuO/Cu2And (3) an O/Cu ternary composite material. The above-mentioned CuO/Cu2The preparation method of the O/Cu ternary composite material utilizes yeast as a micro chemical reactor, is used as a carbon source in the carbothermic synthesis process, can regulate and control the shape of a precursor, and has the advantages of simple process and short synthesis period.
Description
Technical Field
The invention relates to the technical field of preparation of composite materials, in particular to CuO/Cu2A preparation method of an O/Cu ternary composite material.
Background
With the increasing severity of the ecological environment crisis, the exploration of multiphase composite materials capable of reducing environmental pollution becomes a hotspot of research in the fields of information, electronics, photocatalysis and the like at present. In the method for removing the pollutants, the photocatalytic degradation can directly convert the pollutants into carbon dioxide and water, and the advantages are obvious. In the photocatalytic degradation process, the irradiation source has important contribution to improving the activity of the catalyst. Most of the traditional photocatalytic reactors adopt expensive ultraviolet lamp light sources, are high in energy consumption, unstable, low in mechanical stability, short in service life, harmful to human bodies and considered as uneconomical light sources; and the use of visible light or near ultraviolet light can save economic cost, and is particularly suitable for large-scale operation. It can be seen that new methods are sought and designedThe visible light driven organic conversion photocatalyst has important significance. Copper oxide (CuO) and cuprous oxide (Cu)2O) is a p-type semiconductor, the band gap widths are respectively 1.2 eV-1.9 eV and 2.0 eV-2.2 eV, and the photocatalyst has the characteristics of low cost, rich resources, no toxicity and the like, but the photocatalytic activity and the stability of the photocatalyst are still to be improved.
Disclosure of Invention
The invention aims to provide CuO/Cu2A preparation method of an O/Cu ternary composite material, which aims to solve the problem of CuO/Cu prepared in the prior art2The technical problem that the O/Cu ternary composite material can not meet the requirements of photocatalytic performance.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
the invention provides a method comprising the following steps: s1, respectively preparing a copper salt solution and an alkali liquor; s2, adding yeast into water for culturing, and adding the yeast into the copper salt solution and the alkali liquor in sequence after culturing to obtain a mixed solution; s3, heating the mixed solution for reaction to obtain a reaction solution; s4, drying the reaction solution, calcining, cooling to room temperature, and calcining again to obtain the CuO/Cu2And (3) an O/Cu ternary composite material.
Further, in the step S2, the mass-to-volume ratio of the yeast to the water is 0.05g/ml to 0.15g/ml, and the concentration of the yeast cells in the cultured solution is 106～107One per ml.
Further, the culture time of the yeast in water is 30-45 min.
Further, in the step S3, the heating reaction of the mixed solution is to heat the mixed solution in a microwave reactor to react, and the heating temperature is 70 ℃ to 90 ℃.
Further, the heating reaction time of the mixed solution is 4-8 min.
Further, the ratio of the quantity concentration of the copper salt solution to the substance concentration of the alkali liquor is 1: 1 to 4.
Further, the step S4 is specifically: drying the reaction solution, calcining at 250-350 ℃ for 0.5-1 h, cooling to room temperature, and then calcining at 450 DEG CCalcining for 0.5-1 h at the temperature of 550 ℃ again, and cooling to obtain the CuO/Cu2And (3) an O/Cu ternary composite material.
Further, the particle size of the ternary composite material prepared by the preparation method is 50 nm-100 nm.
The invention provides CuO/Cu2The preparation method of the O/Cu ternary composite material comprises the steps of culturing yeast in water, allowing the yeast to grow, and allowing divalent copper ions to enter yeast cells and react with alkali to generate a precursor copper hydroxide; the yeast is used as a micro-reactor, the concentration of reactants can be controlled, the reaction space is controlled, and the particle growth is limited; during the calcination process, the cell wall can be converted into carbon to be wrapped on the surface of the precursor, the carbon thermal reduction reaction is carried out, and the particle appearance and the size of the generated ternary composite material are controlled. The preparation method utilizes the yeast as a micro chemical reactor, is used as a carbon source in the carbothermic synthesis process, can regulate and control the shape of the precursor, and has simple process and short synthesis period.
Drawings
FIG. 1 shows CuO/Cu prepared in example 1 of the present invention2X-ray diffraction pattern of the O/Cu ternary composite material;
FIG. 2 shows CuO/Cu prepared in example 1 of the present invention2Scanning electron microscope pictures of the O/Cu ternary composite material;
FIG. 3 shows CuO/Cu prepared in example 2 of the present invention2X-ray diffraction pattern of the O/Cu ternary composite material;
FIG. 4 shows CuO/Cu prepared in example 2 of the present invention2Scanning electron microscope pictures of the O/Cu ternary composite material;
FIG. 5 shows CuO/Cu prepared in example 3 of the present invention2X-ray diffraction pattern of the O/Cu ternary composite material;
FIG. 6 shows CuO/Cu prepared in example 3 of the present invention2Scanning electron microscope pictures of the O/Cu ternary composite material;
FIG. 7 shows CuO/Cu prepared in examples 1 to 52The ultraviolet absorption spectrogram of the O/Cu ternary composite material applied to photocatalytic degradation of organic methylene blue, wherein the first chart is a chart without CuO/Cu addition2And a control group of the O/Cu ternary composite material is used for an ultraviolet absorption spectrogram of photocatalytic degradation organic matter methylene blue.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
The method is completed under the subsidies of excellent youth projects (project approval number: 17B138) of the education hall in Hunan province and natural science fund (project approval number: 2018JJ3251) in Hunan province.
The invention provides a CuO/Cu2The preparation method of the O/Cu ternary composite material comprises the following steps: s1, respectively preparing a copper salt solution and an alkali liquor; s2, adding yeast into water for culturing, and adding the yeast into the copper salt solution and the alkali liquor in sequence after culturing to obtain a mixed solution; s3, heating the mixed solution for reaction to obtain a reaction solution; s4, drying the reaction solution, calcining, cooling to room temperature, and calcining again to obtain CuO/Cu2And (3) an O/Cu ternary composite material.
In order to obtain CuO/Cu having a good charge separation structure, visible light absorption characteristics and reactive sites2A great deal of research is carried out on an O/Cu ternary composite material by technical personnel, for example, a surface plasma resonance co-catalyst is combined on the surface of the ternary composite material, so that the recombination of photogenerated electrons and holes can be effectively inhibited, and the energy conversion efficiency of a photocatalytic material is greatly improved. Synthesis of CuO/Cu by sol-gel method, chemical vapor deposition method, sonochemical method or hydrothermal method2O, CuO and Cu2The synergistic effect of O and the surface plasma resonance effect of Cu on the surface of the CuO/Cu2O photocatalyst explain the enhancement of the catalytic activity. Specific examples are Mosleh S, Rahimi M R, Ghaedi M, et al, Sonochemical-assisted synthesis of CuO/Cu2O/Cu nanoparticles as efficient photocatalyst for simultaneous degradation of pollutant dyes in rotating packed bed reactor:LED illumination and central composite design optimization[J]Ultrastronics sonochemistry 2018,40:601-2O/Cu nano-meterParticles, which were found to have good photocatalytic properties; zhao Y, Zhang Y, Zhao H, et al2O/CuO core-shell nanowire heterostructures for lithium-ion batteries[J]Nano Research 2015,8(8):2763-2The O/CuO core-shell nanowire heterostructure was found to have excellent lithium battery performance. However, the above preparation of Cu/Cu2Most methods of O/CuO composite materials require complex equipment or complex processes, toxic raw materials and solvents, and have low yield.
Yeast is a simple unicellular fungus, belongs to facultative anaerobes, can survive in aerobic and anaerobic environments, is low in price and easy to survive. The basic structure of yeast cell is mainly five parts of cell wall, cytoplasm, cell membrane, nucleus and vacuole, the cell structure of yeast is simple, its interior has many precise reactors, and can produce many chemical reactions, the signal transmission is passed through the grid structure in the reactor, and the cell itself can be regulated and controlled by these reactions, and finally make action suitable for reaction. Finally, the reaction which is not related to the physiological performance of the cell can be carried out in the cell, a product with excellent performance is obtained, and the yeast cell provides a good reaction platform.
The invention provides CuO/Cu2The preparation method of the O/Cu ternary composite material comprises the steps of culturing yeast in water, allowing the yeast to grow, and allowing divalent copper ions to enter yeast cells and react with alkali to generate a precursor copper hydroxide; the yeast is used as a micro-reactor, the concentration of reactants can be controlled, the reaction space is controlled, and the particle growth is limited; during the calcination process, the cell wall can be converted into carbon to be wrapped on the surface of the precursor, the carbon thermal reduction reaction is carried out, and the particle appearance and the size of the generated ternary composite material are controlled.
The invention utilizes yeast as a microchemical reactor and a carbon source to prepare CuO/Cu by a carbothermic method2The shape of the precursor can be regulated and controlled by yeast, and the yeast is synthesizedSimple process operation, good repeatability, high yield, simple process compared with the method and short synthesis period.
Further, in step S2, the mass-to-volume ratio of yeast to water is 0.05g/ml to 0.15g/ml, and the concentration of yeast cells in the solution after culture is 106～107One per ml. The culture time of the yeast in water is 30-45 min. The invention adopts the dried yeast powder which grows after being cultured in water, and the shriveled cells in the dried yeast powder can also be recovered. The mass-volume ratio of yeast to water is mainly controlled by controlling the concentration of the reaction raw materials.
Further, the yeast is active dry yeast.
Further, in step S3, the heating reaction of the mixed solution is to heat the mixed solution in a microwave reactor to react, wherein the heating temperature is 70 ℃ to 90 ℃. The traditional heating method has temperature gradient, and the heat quantity is from outside to inside. The invention adopts microwave-assisted heating, the heat is generated from the inside, the heating is rapid and uniform, no temperature gradient exists, the energy is saved, the efficiency is high, and the control is easy, so that the granularity of the precursor product can be uniform. Furthermore, the heating reaction time of the mixed solution is 4-8 min. The time for heating the mixed solution has an influence on the particle size of the precursor copper hydroxide. The reaction time is too long, and the granularity of the copper hydroxide is too large; the reaction time is too short, so that the reaction is not uniform and incomplete.
Further, the ratio of the quantity concentration of the copper salt solution to the alkaline solution is 1: 1 to 4. The divalent copper ions enter the yeast cells and react with the alkali liquor to generate a precursor copper hydroxide. When the copper salt is excessive, part of the copper ions form precipitated Cu (OH)2(ii) a When the alkali liquor is excessive, the copper hydroxide precipitate is dissolved in the alkali liquor to generate Cu (OH)4 2-. Both of the above conditions affect the yield to some extent.
Further, step S4 is specifically: the reaction solution is dried and calcined for 0.5h to 1h at the temperature of 250 ℃ to 350 ℃, cooled to room temperature, then calcined again for 0.5h to 1h at the temperature of 450 ℃ to 550 ℃, and cooled to obtain CuO/Cu2And (3) an O/Cu ternary composite material. Calcining the dried reaction liquid at 250-350 ℃ to calcine the yeast to generate carbon and wrap the carbon on the surface of the precursor;and calcining again at 450-550 ℃ after cooling, so as to fully perform carbothermic reduction reaction and remove residual carbon.
Furthermore, the particle size of the ternary composite material prepared by the preparation method is 50 nm-100 nm. CuO/Cu prepared by the invention2The particle size of the O/Cu ternary composite material is about 50-100 nm, and the nano-sheets are combined into a nano-flower-shaped structure under the condition of no agglomeration.
The chemicals used in the following examples are all commercially available. The yeast is Angel brand high-activity dry yeast powder.
Example 1
In this example, CuO/Cu2The preparation method of the O/Cu ternary composite material comprises the following steps:
s1, mixing 2.5g of analytically pure copper sulfate pentahydrate (CuSO)4〃5H2O) was added to 20mL of deionized water to prepare a copper sulfate solution having a concentration of 0.5 mol/L. 0.8g of analytically pure sodium hydroxide was dissolved in 20mL of deionized water to prepare a 1.0mol/L sodium hydroxide solution.
S2, adding 2.0g of yeast powder into 20mL of deionized water for culturing for 30min, adding the yeast powder into a copper sulfate solution after the culture is finished, and gradually dropwise adding the mixed solution into a sodium hydroxide alkali solution to obtain a mixed solution.
S3, placing the mixed solution obtained in the step S2 in a microwave reactor, and reacting at the temperature of 80 ℃ for 5min to obtain a reaction solution.
S4, centrifuging the reaction solution at the rotating speed of 5000rpm and drying the reaction solution in a drying box at the temperature of 80 ℃ for 12 hours. And drying the reaction liquid to obtain a solid sample, grinding the solid sample, putting the ground solid sample into a crucible with a cover, putting the crucible into a resistance furnace, calcining at 300 ℃ and keeping the temperature for 1h, cooling to room temperature, and grinding again. Putting the ground sample into a crucible with a cover again, putting the crucible into a resistance furnace for secondary calcination, keeping the calcination temperature at 500 ℃ for 1h, cooling to room temperature, and grinding to obtain the CuO/Cu2And (3) an O/Cu ternary composite material. CuO/Cu2The yield of the O/Cu ternary composite material is 59.6 percent.
The CuO/Cu prepared in this example was used2Performing X-ray diffraction detection and scanning electron microscope detection on the O/Cu ternary composite materialRefer to fig. 1 and 2, respectively. As can be seen from FIG. 1, CuO and Cu are present in the composite material prepared in this example2Three phases of O and Cu prove that the sample prepared in the example is CuO/Cu2And (3) an O/Cu ternary composite material. As can be seen from FIG. 2, the CuO/Cu prepared in this example2The O/Cu ternary composite material has an agglomeration phenomenon because the amount of yeast is relatively small, and the dispersion effect of the yeast in a precursor synthesis stage is poor; in the calcination stage, less gas is generated, so that the pores are less and the agglomeration is serious.
Example 2
In this example, CuO/Cu2The preparation method of the O/Cu ternary composite material comprises the following steps:
s1, mixing 2.5g of analytically pure copper sulfate pentahydrate (CuSO)4〃5H2O) was added to 20mL of deionized water to prepare a copper sulfate solution having a concentration of 0.5 mol/L. 0.8g of analytically pure sodium hydroxide was dissolved in 20mL of deionized water to prepare a 1.0mol/L sodium hydroxide solution.
S2, adding 2.5g of yeast powder into 20mL of deionized water for culturing for 40min, adding the yeast powder into a copper sulfate solution after the culturing is finished, and gradually dropwise adding the mixed solution into a sodium hydroxide alkali solution to obtain a mixed solution.
S3, placing the mixed solution obtained in the step S2 in a microwave reactor, and reacting at the temperature of 70 ℃ for 8min to obtain a reaction solution.
S4, centrifuging the reaction solution at the rotating speed of 5000rpm and drying the reaction solution in a drying box at the temperature of 80 ℃ for 12 hours. And drying the reaction liquid to obtain a solid sample, grinding the solid sample, putting the ground solid sample into a crucible with a cover, putting the crucible into a resistance furnace, calcining at 250 ℃ and keeping the temperature for 1h, cooling to room temperature, and grinding again. Putting the ground sample into the crucible with the cover again, putting the crucible into a resistance furnace for secondary calcination, keeping the calcination temperature at 450 ℃, keeping the calcination temperature for 1h, cooling to room temperature, and grinding to obtain the CuO/Cu2And (3) an O/Cu ternary composite material. CuO/Cu2The yield of the O/Cu ternary composite material is 62.8 percent.
The CuO/Cu prepared in this example was used2And (3) carrying out X-ray diffraction detection and scanning electron microscope detection on the O/Cu ternary composite material, and respectively referring to fig. 3 and fig. 4. As can be seen from FIG. 3, this example was preparedTo the composite material contains CuO and Cu2Three phases of O and Cu prove that the sample prepared in the example is CuO/Cu2And (3) an O/Cu ternary composite material. As can be seen from FIG. 4, the CuO/Cu prepared in this example2The particle size of the O/Cu ternary composite material is about 100nm, the nano sheets are firstly combined, and then the nano sheets are combined into a shape similar to a rose, a nano flower-shaped structure is formed, and the size of the nano flower structure is about 600 nm-700 nm.
Example 3
In this example, CuO/Cu2The preparation method of the O/Cu ternary composite material comprises the following steps:
s1, mixing 2.5g of analytically pure copper sulfate pentahydrate (CuSO)4·5H2O) was added to 20mL of deionized water to prepare a copper sulfate solution having a concentration of 0.5 mol/L. 1.6g of analytically pure sodium hydroxide was dissolved in 20mL of deionized water to prepare a 2.0mol/L sodium hydroxide solution.
S2, adding 3.0g of yeast powder into 20mL of deionized water for culturing for 45min, adding the yeast powder into a copper sulfate solution after the culture is finished, and gradually dropwise adding the mixed solution into a sodium hydroxide alkali solution to obtain a mixed solution.
S3, placing the mixed solution obtained in the step S2 in a microwave reactor, and reacting for 4min at the temperature of 90 ℃ to obtain a reaction solution.
S4, centrifuging the reaction solution at the rotating speed of 5000rpm and drying the reaction solution in a drying box at the temperature of 80 ℃ for 12 hours. And drying the reaction solution to obtain a solid sample, grinding the solid sample, putting the ground solid sample into a crucible with a cover, putting the crucible into a resistance furnace, calcining at 350 ℃, keeping the temperature for 0.5h, cooling to room temperature, and grinding again. Putting the ground sample into the crucible with the cover again, putting the crucible into a resistance furnace for secondary calcination, keeping the calcination temperature at 550 ℃, keeping the calcination temperature for 0.5h, cooling to room temperature, and grinding to obtain the CuO/Cu2And (3) an O/Cu ternary composite material. CuO/Cu2The yield of the O/Cu ternary composite material is 61.3 percent.
The CuO/Cu prepared in this example was used2And (3) carrying out X-ray diffraction detection and scanning electron microscope detection on the O/Cu ternary composite material, and respectively referring to fig. 5 and fig. 6. As can be seen from FIG. 5, CuO and Cu are present in the composite material prepared in this example2Three phases of O and Cu prove that the sample prepared in the example is CuO/Cu2And (3) an O/Cu ternary composite material. As can be seen from FIG. 6, the CuO/Cu prepared in this example2The particle size of the O/Cu ternary composite material is about 50 nm-100 nm, the particles have an agglomeration phenomenon, but the stacking structure is irregular.
Example 4
In this example, CuO/Cu2The preparation method of the O/Cu ternary composite material comprises the following steps:
s1, 1.7g of analytically pure copper chloride dihydrate (CuCl)2·2H2O) was added to 20mL of deionized water to prepare a 0.5mol/L copper chloride solution. 1.12g of analytically pure potassium hydroxide was dissolved in 20mL of deionized water to prepare a 1.0mol/L potassium hydroxide solution.
S2, adding 3.0g of yeast powder into 20mL of deionized water for culturing for 45min, adding the yeast powder into a copper chloride solution after the culture is finished, and gradually dropwise adding the mixed solution into a potassium hydroxide solution to obtain a mixed solution.
S3, placing the mixed solution obtained in the step S2 in a microwave reactor, and reacting at the temperature of 80 ℃ for 5min to obtain a reaction solution.
S4, centrifuging the reaction solution at the rotating speed of 5000rpm and drying the reaction solution in a drying box at the temperature of 80 ℃ for 12 hours. And drying the reaction liquid to obtain a solid sample, grinding the solid sample, putting the ground solid sample into a crucible with a cover, putting the crucible into a resistance furnace, calcining at 300 ℃ and keeping the temperature for 1h, cooling to room temperature, and grinding again. Putting the ground sample into a crucible with a cover again, putting the crucible into a resistance furnace for secondary calcination, keeping the calcination temperature at 500 ℃ for 1h, cooling to room temperature, and grinding to obtain the CuO/Cu2And (3) an O/Cu ternary composite material. CuO/Cu2The yield of the O/Cu ternary composite material is 55.9 percent.
Example 5
In this example, CuO/Cu2The preparation method of the O/Cu ternary composite material comprises the following steps:
s1, 2.416g of analytically pure copper nitrate trihydrate (Cu (NO)3)2·3H2O) was added to 20mL of deionized water to prepare a 0.5mol/L copper nitrate solution. 1.12g of analytically pure potassium hydroxide are dissolved1.0mol/L potassium hydroxide solution is prepared in 20mL deionized water.
S2, adding 3.0g of yeast powder into 20mL of deionized water for culturing for 45min, adding the yeast powder into a copper nitrate solution after the culture is finished, and gradually dropwise adding the mixed solution into a potassium hydroxide solution to obtain a mixed solution.
S3, placing the mixed solution obtained in the step S2 in a microwave reactor, and reacting at the temperature of 80 ℃ for 5min to obtain a reaction solution.
S4, centrifuging the reaction solution at the rotating speed of 5000rpm and drying the reaction solution in a drying box at the temperature of 80 ℃ for 12 hours. And drying the reaction liquid to obtain a solid sample, grinding the solid sample, putting the ground solid sample into a crucible with a cover, putting the crucible into a resistance furnace, calcining at 300 ℃ and keeping the temperature for 1h, cooling to room temperature, and grinding again. Putting the ground sample into a crucible with a cover again, putting the crucible into a resistance furnace for secondary calcination, keeping the calcination temperature at 500 ℃ for 1h, cooling to room temperature, and grinding to obtain the CuO/Cu2And (3) an O/Cu ternary composite material. CuO/Cu2The yield of the O/Cu ternary composite material is 60.8 percent.
CuO/Cu prepared in examples 1 to 52The O/Cu ternary composite material is applied to an experiment for degrading organic matters through photocatalysis. The experimental procedure was as follows: taking the CuO/Cu prepared in the example 1-520.1g of each O/Cu ternary composite material is respectively added into 20mL of methylene blue solution with the concentration of 20mg/L, the mixture is put into a glass test tube, and 0.3mL of hydrogen peroxide with the concentration of 30 wt% is respectively added into each test tube. The test tube is placed into a Bilang BL-GHX-V optical reactor, and a xenon lamp with the lamp intensity of 1kw is turned on to carry out the photocatalytic reaction. After 40min of illumination, each tube was placed in a centrifuge and centrifuged at 13000r/min for 5min, the supernatant in the tube was pipetted into a cuvette using a rubber-tipped dropper, and the absorbance was measured in an ultraviolet-visible spectrophotometer (Nissan, UV-2501), respectively. Control group did not add CuO/Cu2The other processes of the O/Cu ternary composite material are the same as the previous processes. The light absorption spectra of examples 1-5 and the control group are shown in FIG. 7, and the specific results are shown in Table 1:
TABLE 1 photodegradation rates of various examples and control
| Examples | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Control group |
| Degradation Rate (%) | 99.33 | 99.60 | 99.63 | 99.02 | 99.36 | 33.23 |
Examples 1 to 5 preparation of the resulting CuO/Cu2The photodegradation rate of the O/Cu ternary composite material applied to photocatalytic degradation of organic methylene blue is shown in Table 1. Illumination is carried out in a Bilang BL-GHX-V optical reactor for 40min, and then CuO/Cu prepared in examples 1-5 is added2The photodegradation rates of the O/Cu ternary composite material are 99.33%, 99.60%, 99.63%, 99.02% and 99.36%, respectively. While the control group had no CuO/Cu added2The degradation rate of methylene blue of the O/Cu ternary composite material only in the presence of hydrogen peroxide is only 33.23 percent. This example demonstrates the preparation of CuO/Cu according to the invention2The O/Cu ternary composite material hasBetter photocatalytic performance.
The above description is only an embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of changes or substitutions within the technical scope of the present invention, and all such changes or substitutions are included in the scope of the present invention. Moreover, the technical solutions in the embodiments of the present invention may be combined with each other, but it is necessary to be able to be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be considered to be absent, and is not within the protection scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (6)
1. CuO/Cu2The preparation method of the O/Cu ternary composite material is characterized by comprising the following steps: the method comprises the following steps:
s1, respectively preparing a copper salt solution and an alkali liquor;
s2, adding yeast into water for culturing, adding the yeast into the copper salt solution after the culturing is finished, and adding the mixed solution of the yeast and the copper salt solution into the alkali liquor to obtain mixed solution;
s3, heating the mixed solution for reaction to obtain a reaction solution; the mixed solution heating reaction is to place the mixed solution in a microwave reactor to be heated for reaction, wherein the heating temperature is 70-90 ℃; the heating reaction time of the mixed solution is 4-8 min;
s4, drying the reaction solution, calcining, cooling to room temperature, and calcining again to obtain the CuO/Cu2And (3) an O/Cu ternary composite material.
2. CuO/Cu according to claim 12The preparation method of the O/Cu ternary composite material is characterized in that in the step S2, the mass-volume ratio of the yeast to the water is 0.05 g/ml-0.15 g/ml, and the concentration of the yeast cells in the cultured solution is 106～107One per ml.
3. CuO/Cu according to claim 12The preparation method of the O/Cu ternary composite material is characterized in that the culture time of the yeast in water is 30-45 min.
4. CuO/Cu according to any one of claims 1 to 32The preparation method of the O/Cu ternary composite material is characterized in that the ratio of the quantity concentration of the copper salt solution to the substance concentration of the alkali liquor is 1: 1 to 4.
5. CuO/Cu according to any one of claims 1 to 32The preparation method of the O/Cu ternary composite material is characterized in that the step S4 specifically comprises the following steps: drying the reaction solution, calcining at 250-350 ℃ for 0.5-1 h, cooling to room temperature, calcining again at 450-550 ℃ for 0.5-1 h, and cooling to obtain the CuO/Cu2And (3) an O/Cu ternary composite material.
6. CuO/Cu according to any one of claims 1 to 32The preparation method of the O/Cu ternary composite material is characterized in that the particle size of the ternary composite material prepared by the preparation method is 50-100 nm.
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